Substituted diphenyl acetate compounds and methods for preparing same



Patented Apr. 16, 1946 UNITED STATES PATENT OFFICE SUBSTITUTED DIPHENYL ACETATE COM- POUNDS METHODS FOR PREPARING SAME Lee C. Cheney, Detroit, and William G. Bywater, Grosse Pointe Woods, Mich, assignors to Parke, Davis & Company, Detroit, Mich., a corporation of Michigan No Drawing. Application June 26, 1944;

Serial No. 542.262

4 Claims. (01. 260-469) The invention relates to the preparation of certain new chemical compounds which are useful as intermediates in the manufacture of more pholino esters having antispasmodic properties. More particularly, this invention relates to a class or compounds having the formula CHCO OCaHnX where X is OH or halogen. This application is a continuation-in-part of our copending application, Serial No. 344.136, flied The invention may be illustrated by the following examples.

Example 1.Preparation of. w-bromohexul diphenylacetate The reaction mixture after cooling may be fur-- ther reacted with morpholine to obtain 6-(4- morpholine) -n-hexyl diphenylacetate hydrochloride as described in our copending application,

' Serial No. 514,162, filed December 13, 1943, as a division of our application, Serial No. 344,136.

B. A suspension of 124 g. (0.496 mole) of finely ground potassium diphenylacetate and 231 g. (0.946 mole; 1.9 equivalents) of hexamethylene bromide in one liter of xylene is refluxed with stirring for 25 hours. The reaction mixture is then cooled and filtered to remove the precipitated potassium bromide. The xylene is distilled at atmospheric pressure and the residue fractionally distilled. In this manner there is secured 107.3 g. (98% recovery or the excess) of hexamethylene bromide and 122 g. (65.6%) of w-broinohexyl diphenylacetate. boiling point 223-6/2.5 .mm.;

and a residue 28 g. (18%) of hexamethylene bisdiphenylacetate. w-Bromohexyl diphenylacetate has the following formula CHCOOCcHnBi' The isolated w-bromohexyl diphenylacetate may be reacted with morpholine to obtain 6-(4- morpholino)-n-hexyl diphenylacetate hydro chloride and the yields thereby obtained are much higher than with the process specifically described in Serial No. 514,162.

Example 2.-Preparation of w-chlorohexyl dtphenylacetate A solution of 20 g. of thionyl chloride in 25 ml. of carbon tetrachloride is added dropwise in one hour to a well stirred solution of 26.3 g. (0.084 mole) of w-hydroxyhexyl diphenylacetate in 100 ml. of carbon tetrachloride with no external cooling. The solution is then refluxed and stirred for 2 hours. The excess thionyl chloride is removed and the product distilled in vacuo, thereby ob-. talning w-chlorohexyl diphenylacetate, boiling point 215-222/2.5 mm.;

yield: 20 g. or 72%. It has the formula Example 3.--Preparation of w-hydroxyheryl diphenylacetate A solution of 115.7 g. (0.5 mole) of diphenylacetyl chloride in 200 ml. of dry acetone is added dropwise with stirring during one hour to a solu- .the reaction mixture yields, after removal of pyridine hydrochloride, 64.4 g. of dark-green product, boiling point 222-232/4 mm. and a residue of 68.8 g. (27.3%) of hexamethylene bisdiphenylacetate. Redistillation oi the crude 2 2,898,410 I product gives 47 g. (29.2%) of light yellow w-hy- What we claim as our invention is:

droxyhexyl diphenyiacetate, boiling point 1. A compound having the formula.

-i I B cncoocanx D where X is a member of the class consisting of b Saponification equivalent calc: 312.4; found: 318, m gg g i fi iig fig stltuted on carbon It has the iormula 2. w-chlorohenl diphenyl'acetate.

Q 3. w-Bromoheml diphenvlacetate.

' h v CHCOOOHBQH 4 m Hydroxyhexyl dip enylacetate 15 LEE C.

CHENEY. WILLIAM G. BYWATm. 

